allyl 2-O-acetyl-3,4-di-O-benzoyl-α-L-rhamnopyranosyl trichloroacetimidate | 224622-44-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: allyl 2-O-acetyl-3,4-di-O-benzoyl-α-L-rhamnopyranosyl trichloroacetimidate
• 英文别名: 2-O-acetyl-3,4-di-O-benzoyl-α-L-rhamnopyranosyl trichloroacetimidate；Bz(-3)[Bz(-4)]Rha2Ac(a)-O-C(NH)CCl3；[(2S,3S,4R,5R,6S)-5-acetyloxy-4-benzoyloxy-2-methyl-6-(2,2,2-trichloroethanimidoyl)oxyoxan-3-yl] benzoate
• CAS: 224622-44-0
• 化学式: C₂₄H₂₂Cl₃NO₈
• 分子量: 558.8
• InChiKey: IOHIAPRTRWMIOI-QJQCEZOGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  36
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  121
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  allyl 2-O-acetyl-3,4-di-O-benzoyl-α-L-rhamnopyranosyl trichloroacetimidate 在 2,4-二甲基吡啶 、 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 、 silver trifluoromethanesulfonate 、 乙酰氯 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 1.67h， 生成 allyl 4-O-<2-O-(2,3,4-tri-O-acetyl-β-L-xylopyranosyl)-3,4-di-O-benzoyl-α-L-rhamnopyranosyl>-2,3,6-tri-O-benzoyl-α-D-mannopyranoside
  参考文献：
  名称：

  Facile Synthesis of a Branched Trisaccharide–The Repeating Unit of Antigen O2 Polymer using Orthoester Formation - Rearrangement Strategy

  摘要：

  The synthesis of a branched trisaccharide, the repeating unit of the antigen O2 polymer containing L-rhamnose, D-mannose, and L-xylose, was achieved using orthoester formation- rearrangement strategy.

  DOI：

  10.1080/07328309908543994
• 作为产物：
  描述：

  allyl 2-O-acetyl-3,4-di-O-benzoyl-α-L-rhamnopyranoside 在 palladium dichloride sodium acetate 、 溶剂黄146 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 allyl 2-O-acetyl-3,4-di-O-benzoyl-α-L-rhamnopyranosyl trichloroacetimidate
  参考文献：
  名称：

  Synthesis of Trisaccharide of Incanoside from Caryopteris incana

  摘要：

  Trisaccharide phenyl 2,3,4,6-tetra-O-acetyl-beta-D-glucopyranosyl-(1 --> 2)-3,4-di-O-benzoyl-alpha-L-rhamnopyranosyl-(1 --> 3 --> 3)-2-O-acetyl-4,6-O-benzylidene-1-thio-beta-D-glucopyranoside, the sugar core of incanosides from Caryopteris incana (T-HUNB.), was synthesized via a concise route. The key step of this route involved the preparation of decisive disaccharide acceptor from the phenyl 2-acetyl-3,4-di-O-benzoyl-alpha-L-rhamnopyranosyl-(1 --> 3)-2-O-acetyl-4,6-O-benzylidene-1-thio-beta-D-glucopyranoside by regioselective and chemoselective deacetylation method.

  DOI：

  10.1081/scc-120027292

文献信息

• Design, synthesis, and immunochemical characterization of a chimeric glycopeptide corresponding to the Shigella flexneri Y O-polysaccharide and its peptide mimic MDWNMHAA
  作者：B. Rehana Hossany、Blair D. Johnston、Xin Wen、Silvia Borrelli、Yue Yuan、Margaret A. Johnson、B. Mario Pinto

  DOI：10.1016/j.carres.2009.03.029

  日期：2009.8

  pentasaccharide corresponding to the S. flexneri Y O-polysaccharide and the octapeptide mimic, MDWNMHAA. Both chimeric molecules consist of a rhamnose trisaccharide linked through an alpha- or beta-thioglycosidic linkage to a MDW moiety in which the W unit has been modified. We predicted that omission of the NMHAA moiety would obviate the bound water molecules that provided complementarity with the antibody-combining

  设计了两种对应于弗氏志贺氏菌Y O-多糖的糖肽嵌合体及其肽模拟物，以试图通过相对于O-多糖的原始八肽模拟物增加结合熵来改善结合亲和力。该设计基于单克隆抗体SYA / J6的X射线晶体结构及其相关配体，对应于弗氏链球菌Y O多糖的五糖和八肽模拟物MDWNMHAA的复合物。两个嵌合分子均由鼠李糖三糖组成，鼠李糖三糖通过α-或β-硫糖苷键连接至其中W单元已被修饰的MDW部分。我们预测，省略NMHAA部分将消除与抗体结合位点互补的结合水分子，以及由于在肽的C-末端施加α-转角而导致的构象限制。然后使用程序自动停靠3.0将糖肽对接至SYA / J6的活性位点，并对其结构进行优化。在每种情况下获得的最佳模型表明，具有α-或β-硫糖苷键的嵌合分子可能是抗体的合理替代配体。我们在这里报告使用溶液和固相策略合成α-糖肽。免疫化学表征表明，不幸的是，α-糖肽没有抑制SYA / J6与弗氏链球菌Y脂多糖的结合。
• Synthesis and conformational analysis of a pentasaccharide corresponding to the cell-wall polysaccharide of the Group A Streptococcus
  作者：Christer Höög、Archimede Rotondo、Blair D. Johnston、B.Mario Pinto

  DOI：10.1016/s0008-6215(02)00218-5

  日期：2002.11

  The synthesis and conformational analysis of a pentasaccharide corresponding to a fragment of the cell-wall polysaccharide (CWPS) of the bacteria Streptococcus Group A are described. The polysaccharide consists of alternating alpha-(1 --> 2)- and alpha-(1 --> 3)-linked L-rhamnopyranose (Rhap) residues with branching 2-acetamido-2-deoxy-D-glucopyranose (GlcpNAc) residues linked beta-(1 --> 3) to alternate

  描述了对应于细菌链球菌A组的细胞壁多糖（CWPS）片段的五糖的合成和构象分析。多糖由交替的α-（1-> 2）-和alpha-（1-> 3）连接的L-鼠李糖（Rhap）残基组成，带有分支的2-乙酰氨基-2-脱氧-D-吡喃葡萄糖（GlcpNAc）残基将β-（1-> 3）连接到交替的鼠李糖环上。五糖作为CWPS上可能的末端单元是令人感兴趣的，用于疫苗中。合成使用三氯乙酰亚胺酸酯糖基供体。在气相和明显存在水的情况下，利用力场CVFF和PARM22对五糖的分子动力学（MD）计算得出了对柔性和优选构象空间的不同预测。还使用HSEA力场进行了蒙特卡洛都会（MMC）计算。实验数据是从一维瞬态NOE测量获得的。将完整的堆积曲线与通过完全松弛矩阵计算获得的曲线进行比较，以得出构象模型。总的来说，实验数据和计算数据之间的最佳拟合是通过使用HSEA力场的MMC模拟获得的。为了比较，还进行了与A组变体多糖相对应的四
• A highly efficient and convergent synthesis of a hexasaccharide, a dimer of the repeating unit of the antigen O2 polysaccharide of Stenotrophomonas maltophilia
  作者：Wei Wang、Fanzuo Kong

  DOI：10.1016/s0008-6215(99)00004-x

  日期：1999.1

  A highly efficient and convergent synthesis of a hexasaccharide, which is a dimer of the repeating unit of the antigen O2 polysaccharide of Stenotrophomonas maltophilia, was achieved via coupling of 2,3,4-tri-O-acetyl-alpha-L-xylopyranosyl bromide with the tetrasaccharide, allyl 4-O-3-O-[4-O-(3,4-di-O-benzoyl-alpha-L-rhamnopyranosyl)-2,3,6-tri-O-benzoyl-alpha-D-mannopyranosyl]-4-benzoyl-alpha-L-rhamnopranosyl}-2,3,6-tri-O-benzoyl-alpha-D-mannopyranoside (18) by the Koenigs-Knorr method followed by deacylation. Compound 18 was readily prepared from the coupling of the disaccharide trichloroacetimidate, 4-O-(2-O-acetyl-3,4-di-O-benzoyl-alpha-L-rhamnopyranosyl)-2,3,6-tri-O-benzoyl-alpha-D-mannopyranosyl trichloroacetimidate (8) with the disaccharide acceptor, allyl 4-O-(2-O-acetyl-4-O-benzoyl-alpha-L-rhamnopyranosyl)-2,3,6-tri-O-benzoyl-alpha-D-mannopyranoside (16), and both 8 and 16 were prepared via the trichloroacetimidate method from simple starting materials. The sole use of acyl protecting groups substantially simplified protection and deprotection, and the allyl group at the reducing end of allyl 4-O-2-O[2,3,4-tri-O-acetyl-beta-L-xylopyranosyl]-3-O-[4-O-(2-O-(2,3,4-tri-O-acetyl-beta-L-rhamnopyranosyl)-3,4-di-O-benzoyl-alpha-L-rhamnopyranosyl)-2,3,6-tri-O-benzoyl-alpha-D-mannopyranosyl]-4-O-benzoyl-alpha-L-rhamnopyranosyl} -2,3,6-tri-O-benzoyl-alpha-D-mannopyranoside 19 allowed further chemical transformation. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Efficient synthesis of a heptasaccharide, the repeating unit of the O-chain lipopolysaccharide produced by Xanthomonas campestris strain 642
  作者：Jianjun Zhang、Jun Ning、Fanzuo Kong

  DOI：10.1016/s0008-6215(03)00080-6

  日期：2003.5

  alpha-L-Rhap-(1 --> 3)-alpha-L-Rhap-(1 --> 2)-alpha--L-Rhap-(1 --> 3)-[beta-D-Xylp-(1 --> 2)-][beta-D-Xylp-(1 --> 4)-]alpha-L-Rhap-(1 --> 3)-alpha-L-Rhap, the repeating unit of the O-chain lipopolysaccharide produced by Xanthomonas campestris strain 642 was synthesized as its methyl glycoside via 3-O-selective glycosylation of methyl alpha-L-rhamnopyranosyl-(1 --> 3)-2,4-di-O-benzoyl-alpha-L-rhamnopyranoside (9) with 2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl-(1 --> 3)-2,4-di-O-benzoyl-alpha-L-rhamnopyranosyl-(1 --> 2)-3,4-di-O-benzoyl-(alpha-L-rhamnopyranosyl trichloroacetimidate (8), followed by dixylosylation with 2,3,4-tri-O-benzoyl-alpha,beta-D-xylopyranosyl trichloroacetimidate (12) and subsequent deacylation. (C) 2003 Elsevier Science Ltd. All rights reserved.